89875-06-9Relevant articles and documents
OXIDATIVE CLEAVAGE OF THE Fe-Fe BOND IN 2 USING FERROCINIUM ION: A FACILE ROUTE TO THE SYNTHETICALLY USEFUL COMPLEXES +
Catheline, Daniel,Astruc, Didier
, p. C11 - C14 (1984)
Complexes of the type +PF6-, 3a-3d, (Fp' = (η5-C5Me5)-Fe(CO)2, solvent = THF, CH3COOCH3, CH3CN, or pyridine) are conveniently prepared by the reaction between Fp'2 and Cp2Fe+PF6-, (Cp = η5-C5H5) in the solvent under ambient conditions.The complexes +PF6-, 3e-3g, (L = CO, PPh3, P(OPh)3) are readily prepared from +.Fp'H is formed by treatment of 3a with NaBH4.Fp'SC(S)NMe2 can be prepared from 3a or 3e and NaSC(S)NMe2.
Piano-stool (pentamethylcyclopentadienyl)iron complexes: Syntheses and simple coordination chemistry
Catheline, Daniel,Astruc, Didier
, p. 1094 - 1100 (2008/10/08)
(Fp′CO)+PF6-, 3e [Fp′ = (η5-C5Me5)Fe(CO)2], is synthesized by reaction of Fp′Br with CO (40 atm) and AlCl3 or by reaction of Fp′2 with Cp2Fe+PF6- in THF under CO (1 atm). Oxidation of Fp′2 with Cp2Fe+PF6- in various coordinating solvents S (THF, acetone, acetonitrile, pyridine) gives (Fp′S)+PF6- (3a-d) in high yields. Reaction of (Fp′THF)+PF6-, 3a, with various ligands L (PPh3, P(OPh)3, CO) gives (Fp′L)+PF6-, 3e-g, in high yields; the reaction fails with olefins. 3a also gives Fp′H, 5, with NaBH4 and Fp′SC(S)NMe2, 6a, with NaS2CNMe2, but 6a is obtained in better yield from 3e. Bimetallic complexes [FpSC(NEt2)-S→Fp′]+PF6-, 6c, and [CpFe(η6-C6Me5CH 2)Fp′]+PF6-, 7, are also obtained by reaction of 3a with FpSC-(S)NEt2 and Cp(η5-C6Me5CH2)Fe, respectively. Photolysis of 3e or (Fp′NCMe)+PF6-, 3c, in CH3CN gives a 80% yield of the thermally stable, air-sensitive complex [Cp′Fe(NCMe)3]+PF6-, 9, as deep purple crystals. Without degassing, this photolytic reaction gives dark red [Cp′Fe(NCMe)2(CO)]+PF6-, 10, also obtained from 9 under 1 atm of CO at 20°C. 9 also reacts with PPh3 to give [Cp′Fe(NCMe)2(PPh3)]+PF6 -, 11, with dppe to give [Cp′Fe(NCMe)(η2-dppe)]+PF6 -, 12, and with cyclooctatetraene (COT) to give [Cp′Fe(η6-COT)]+PF6-, 13. The reaction of CO with 11 and 12 gives respectively [Cp′Fe(CO)2(PPh3)]+PF6 -, 3f, also obtained from 3e and PPh3 in refluxing acetone, and [Cp′Fe(CO)(η2-dppe)]+PF6-, 15. Fp′-K+, 16a, obtained from Fp′2 and K mirror, gives Fp′CH3, 17, upon alkylation with CH3I and Fe′-Na+, 16b, obtained from Fp′2 and Na/Hg, gives Fp′CH2OCH3, 18, upon alkylation with ClCH2OCH3.
